Dye-pad, hot-chemical-treatment dyeing process



United States Patent 3,184,284 DYE-PAD, HOT-CHEMICAL-TREATMENT DYEING PROCESS Erik Kissa, Wilmington, Del., assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed Apr. 11, 1963, Ser. No. 272,220 4 Claims. (Cl. 8--54.2)

The present invention is directed to novel dyeing processes for the application of quinoxaline fiber-reactive dyes to cellulosic materials wherein the fabric is padded, optionally dried, treated with hot alkali and washed. The novel processes afford significantly uniform results in the dyeing of all reactive dyes containing a 2,3-dichloro-6- quinoxalinecarbonylamino group and amino dye bases. The dyes employed in the present processes are more fully described in the specification which follows.

With fiber-reactive dyes, it is a well known fact that time, temperature and nature and concentration of acid acceptor are the variables which are important for reaction with the cellulosic textile materials. Although it is possible with all fiber-reactive dyes to get some dye-fiber reaction by varying these variables over an extremely wide range, it is well known that the reactivity among the various reactive dye types, and even among the dyes of the same type, cannot be predicted. Thus, if possible, it is necessary and of advantage to determine for each type of reactive dye a unique method of dyeing, which is compatible with all of the dyes of that type.

In other words, since it is impossible to predict dyeing characteristics from chemical composition, one must find the unique and novel dyeing method for each reactive dye type.

It is, therefore, an object of the present invention to provide, for the first time, dye-pad, hot-chemical-treatment dyeing processes for the two-bath dyeing application of a most recent type of fiber-reactive dyes, those which contain a 2,3-dichloro-6-quinoxalinecarbonylamino group.

Such a method must be compatible with all dyes which' contain said group, and must achieve the significant results described herein.

It is a further object of this invention to provide dyepad, hot-chemical-treatment processes for dyeing said dichloroquinoxaline dyes by either continuous or batch operations in which Williams or jig dyeing equipment, respectively, can be used. A Williams dyeing unit is described in The Application of Vat Dyes, pages 119-120, Americal Association of Textile Chemists and Colorists Monograph No. 2, 1953, Mack Printing Company, Easton, Pennsylvania. A dye jig unit is also illustrated in the same Monograph on page 109.

Still a further object of this invention is to provide processes for obtaining attractive and fast dyeings in high fixation yields, said dyeings reflecting good wash-fastness properties, resistance to acid perspiration and fully acceptable light fastness.

These and other objects of the invention will become apparent in the following description and claims.

The novel processes of dyeing embodied by this invention are characterized by padding the dye solution onto the fabric, optionally drying, treating the padded fabric with a hot aqueous solution of electrolyte and acid ac- "ice ' ceptor, and washing the dyed fabric. More specifically,

the present invention comprises the following combination of steps:

(1 the cellulosic material is padded with said dichloroquinoxaline dye from an aqueous solution thereof maintained at pH 6 to 7.8. Urea is often advantageously added to this padding solution. The dye-padded fabric is then dried, if desired, or is passed directly into the hot-chemical bath;

(2) the dye-padded fabric is treated for at least five seconds with an aqueous alkaline liquor comprising 2 to 15 g./l. of sodium hydroxide and 200 to 300 g./l. of electrolyte selected from the group consisting of NaCl and Na SO the temperature of said liquor being to 218 F.;

(3) the dyed fabric from step (2) is washed for re moval of salts and any unfixed dye, as normally performed by one skilled in the art of dyeing.

There are various ways of operating the novel dye-pad, hot-chemical-treatment processes outlined above.

When the fabric is dried, following the dye-pad step, the residence time of the fabric in the hot-chemical-treatment bath is usually 5 to 10 seconds. A longer time period may be used without harm to the dyeing, but more time than that mentioned is not required to obtain high fixation yields. This modification of the invention affords a continuous process which assures high speed dyeing, being a definite advantage in the trade when long yardages of goods are being dyed.

On the other hand, when short yardages of goods are being dyed, it is sometimes convenient to adapt the dye pad, hot-chemical-treatment process of this invention to the well known jig equipment for the hot-chemical-treatment step. In this modification of the invention, one operates the two liquid treatments with or without intermediate drying of the fabric. Since the time factor can be varied conveniently over a wide range in the jigger, depending on the number of times the fabric is passed through the hot chemical bath, it is convenient to operate at temperatures as low as 80 F. and extend the number of passes of cloth through the alkaline liquor. Generally, 2 or 4 passes, or ends, are sufficient to obtain excellent fixation of the quinoxaline dyes. When the hot chemical treatment is performed in the jig and the quinoxaline dyes are applied together with other types of fiber-reactive dyes which are slower to react with the fiber, the number of passes would be increased to 6, or even more.

The present novel processes afford combinations of the following technically significant features:

(a) Compatibility-all of the dyes which contain a 2,3- dichloro-6-quinoxalinecarbonylamino group can be applied without sacrificing any of the desired application properties of one specific dye.

(b) H igh-fixation-thus economy; since one obtains efficient utilization of the reactive dye.

(c) Convenience-The process can be operated in dye houses which do not have continuous steaming equipment but are equipped with jigs and/or Williams units.

(d) Good fastness properties are maintained by this method.

In order to take full advantage of all of the features of this invention, the described processes must be operated in the defined limits during the hot alkaline treatment. For

instance with certain dyes weaker alkali, or lower. temperatures or shorter times are effective, but to have a reproducible dyeing and compatibility of .all the quinoxaline dyes, the preferred ranges must be maintained. Long times e.g. beyond about seconds during alkaline, treatments are of course impractical in continuous operations. Temperatures higher than the boiling point of the alkaline liquonabout 218 F., are impossible to obtain without special equipment. Stronger alkali than g./l.

of sodium hydroxide lowers fixation and at times depreciates the fastness properties of the dyeing.

. It will berundersto'od by those'skill'ed in the art that additives, for example surface activea'gents and migration inhibitors, and dyeing aids, are sometimes usedin the practice of this invention. .Typicaladditives are:

Urea

New Jersey) 7 Cassofix ASbenzol derivative and resin precondensate Ke1tex--sodium salt of alginic acid (Kelco (30;, Clark,

(1962 AATCC Yearbook p. El -205) (Sou-Tex Chemi cal Co., Inc., Mount Holly, N.C.) 7 Representative examples illustrating the present invention follow: V .7 v

" PART I-DYEING Example I;

Twenty partsof the quinoxaline dye of the structure" are dissolved at 6.2 in 1000:v parts of water.

solution is-padded at 7 8 -F. onto cotton poplin at 65% pickup. The fabric is dried in a fluedryer. Passed with a residence time of five seconds through a 172;F. aqueous bath containing,12 gQ/l. of sodium, hy roxide and D g./l. of sodium sulfate, Washed- (hotwater rinse, cold Water rinse, hot soap scour, hot water rinse and cold water rinse, inturn) anddried. There results a brightred shade which is fast to washing, acid perspiration and light. I V

Example-ll The padded material of ExampleI without drying is passed on a jig for 2 ends of live minutes each (the immersion time is four seconds for 'each end), through an aqueous liquor-at 160 F. (4: l, cl th: liquor ratio) containing 2 g./l. of sodium hydroxide and 300 g./l. sodium sulfate,

tre dissolved at pH 7.2 in 1000 parts of Water containing 30 parts of. Gassofix AS? and 150. parts of urea. This iOllltlOll is .padded at pickup-onto cotton broad- :loth. The impregnated. fabric is dried overheated cans,

raised with a residence timeof seven seconds through a' cotton twill, a dyeing similar to "that'obtainedin Example 1 washed and dried. There results a dyeing o f similar shade, strength and fastness tothat obtainedin Examplej l.

obtained inExarnple VII. 7 U

210 F. aqueous bath containing 10 g./l. of sodium carbonate, 2 g./l. sodium hydroxideand 200 g./l..of sodium sulfate, washed and dried. The resulting ruby shade is fast t'o'washing and light.

Example IV .One yard of the dye-impregnated wet fabric of Example 111 is passed twice (the immersion time for each pass is three seconds) through a 218- F. aqueous bath (10:1

liquor2fabric ratio) containing 15 g./l. of sodium-hydroxide, 150.g./l. of sodium chloride and g./l. of sodium sulfate, washed and dried to give a dyeing similar to that from ExampleIlI. H u. v

V 7 Example V I Twenty-five parts of the quinoxaline dye of the, structure are dissolved at in 11,000 partshof water.' This solution is padded at 70 pickup. onto cotton twill. The fabric is dried and passed .with a residencetime of ten seconds through a 190-=F. aqueous solution of 5 g./ 1. of

sodium hydroxide,- l00 'g./-l. of sodium chloride. and 150 ,g./,1. of sodium"sulfa'te,.washed and ,dried. ,There results ,a bright blue dyeing which is-fast to washing and light.

Exampleyr" One thousandyards of the dye-impregnatedrtwill-from Example V are passed forsix ends- (20 minutes per: end,

' -immersion time 2.5 seconds per end) through an aqueous .80? F; solution'of' 5' g;/l. of sodium hydroxide and 200 g./ l.' ofsodium chloride; 'Afterwashingand drying the V is obtained. a V -E I -H V Twenty partsof thedyeof the structure, I

" jams). i i

' G.nPc'(S0:NH2)b aredissolvedin 1000 parts of water." Thissolution is padded onto one yard of cotton poplin "at-68% pickup. V The poplin fabric i passed" for foure'nds (3 seconds for each pass)--through a F; aqueous so1uti'on"(4:1 'liquorzfabric ratio) 'containing -5' g./l; of sodium hydroxide and 250 g./l. of sodium sulfate, washed and dried, There-results a torquoise' shade which is fast to washing and-light. r s v a a Y .ampleVIIis dried, passed With a residence time-of five sec- Oi dfih 1 F- aq i a h, c nt i ng 0. -l

of sodium hydroxide and 270 g./ l, of sodium chloride,

washed and dried. There results adyeing similar to. that PART ll PREPARATIONOF REACTIVE .As shown in the preceding'examples, process-of the present invention .gives good dyeing s regardless of the type of dye chromophore which is attached to the 2,3-dichloro-6-quinoxalinecarbonylamino group. It has been found that a large variety of said quinoxaline dyes can be used in the invention. This variety is illustrated further by the following examples, numbers 1 through 8 which disclose the preparation of dyes which are applicable in the novel dyeing process.

Example 1 42 parts of an azo-dye base having the following formula H0 8 CH;

are dissolved in 700 parts of water at 40 C. to give a yellow solution. After adjusting the pH to 7.5-8 (using sodium carbonate), 30 parts of finely powdered 2,3-dichloro-6-quinoxalinecarbonyl chloride are added, and the mixture is stirred overnight while maintaining a temperature of 35 40 C. and a pH of 7.5-8 by the addition of sodium carbonate. The yellow solution is then clarified by filtration, salted with 10 parts of sodium sulfate, and the precipitated solid is filtered and washed with a 12% sodium sulfate solution. The filter cake is pressed to 58% dye content, and dried as a thin layer in an oven at 80 C. for 24 hours. The dried product is then ground to a free-flowing light-yellow powder. This powder contains approximately 82% dye, -1'l% water, and 7% Na SO by weight. The dye has the formula and dyes cotton by the above procedure in yellow shades.

Example 2 To 120 parts of 2,4-diaminobenzenesulfonic acid in 1000 parts of water at 35 C. and pH 7.5-8 (maintained using dilute sodium hydroxide solution) are added added to a solution consisting of 150 parts of 10 N sulfuric acid, 110 parts of 5 N sodium nitrite and 500 parts of water. After completion of the addition, the reaction is stirred at 5-15 C. for 4 hours, the excess nitrite is destroyed by the addition of sulfarnic acid, as shown by a negative test on starch iodide paper, the solid is allowed to settle, and about 10,000 :parts of the water layer are removed by decanting.

To the remaining slurry is added a solution consisting of 161 parts of 1-(2',5-dichloro-4-sulfophenyl-3-methyI-S-pyrazolone dissolved in 450 parts of water at pH 7.0 (obtained by adding sodium hydroxide as necessary) and this bright yellow slurry is stirred at pH 4.5-6 (adding sodium acetate as needed) to effect complete solution. The pH of the brown yellow solution is adjusted to 8.2 with sodium hydroxide, the temperature is increased to 40-45 C., and sodiumsulfate is slowly added to salt the solution. The precipitated yellow solid is filtered,

washed with 20% sodium sulfate solution, and dried at 60 C. The dye thus obtained has the formula:

To 500 parts of water are added 188 parts of 2,4-diaminobenzenesulfonic acid and parts of 30% sodium hydroxide. This slurry is stirred to effect solution, cooled to 25 C., and diluted with 1400 parts of water. To this solution are added all at once 112 parts of acetic anhydride and stirring is continued 1 hour, after which the pH is adjusted to 8:05, and 69 parts of a 31% sodium nitrite solution are added. This solution is then added, over /2 hour, to a solution of 500 parts of water, 500 parts of ice, and parts of 30% hydrochloric acid. The resulting slurry is stirred for /2 hour before the excess nitrite is destroyed with sulfamic acid as shown by a negative test on starch iodide paper. This diazo slurry is added with stirring at 5-15 C. over 1 hour to a solution of 500 parts of water, 323 parts of 1-(2-5'-dichloro 4'-sulfophenyl)-3-methy1-5-pyrazolone, 72 parts of 30% sodium hydroxide, 100 parts of sodium acetate, and 500 parts of ice. To this yellow-brown solution are added 120 parts of hydrochloric acid, the temperature is then raised to 90 C. over 1 hour, held at this temperature for 2 hours, cooled to 40 C., and the precipitated solid dyebase is collected by filtration and washed with a dilute hydrochloric acid solution.

This wet dye-base cake is dissolved in a solution of 5000 parts of water and 165 parts of sodium hydroxide. To this rapidly-stirred solution at 30-35 C. are added 230 parts of 2,3-dichloro-6-quinoxalinecarbonyl chloride dissolved in 700 parts of xylene. This mixture is stirred for 3 hours at 35 -40 C., while maintaining the pH at 5.5-8.0 by the addition of a sodium hydroxide solution. The reaction mass is then clarified by filtration, parts of potassium chloride in 2000 parts of water are added over 1 hour, and the precipitated insoluble (in cold water, slightly soluble in boiling water) potassium salt of the formula:

is filtered. This wet press cake is prepared for commercral use by drying below 60 0., adding 4.2% K 80 based on weight of dye, and grinding.

Example 4 26 parts of 2,S-dichloro-6-quinoxalinecarbonyl chloride dissolved in 70 parts of xylene are added to a rapidly stirred solution ,of 37.5 parts of H 'acid-(8-amino-1-naphthol-3,'6-disulfonic. acid) at pH .16 (adjusted withv sodium hydroxide) in 400 parts of 35C. water. Themixture, which converts to a greenish gel, is stirred at 25 35 Cr.

and at pH 4-5 (maintained with sodium hydroxide) for 1 3-4 hours. 720 parts of water are added and the pH is adjusted to 8.5 :02 withsodium hy'droxide. The reaction mass -is thenclarified by filtration and the filtrate is cooled to 515f C. To this brownish solution is added at 5- l5'C. and at pH 7,510.2 j(maintained with sodium hydroxide) over a 1-hour period the vcold diazo I slurry prepared in the usual manner from 130 parts of water, 22.5 parts of orthanilic acid, 5.9 parts of hydrochloric acid, 9.0 parts of sodium nitrite, and 100 parts of ice. This coupling requires 2-3 hours. The red dye of the structure,

NaOa'S sulfate solution, dried below 100 C. in an oven, and. standardized to 65% active ingredient lay-intimate mixing. with sodium sulfate. a 1

- i Examplefi 50.3 parts of the azo-dye base S0 11 no (prepared by coupling acetyl followed by hydrolysis) are dissolved in 1100 parts of. water at pH 7 -7.5 (using sodium hydroxide) and 28.6 parts a of 2,3-dichloro-6-quinoxalinecarbonyl chloride dis: solved in 80-parts ofxylene are a'dded. The resulting mixture is vigorously stirredat pH '6-8 (maintaine'd With s 1' sodium hydroxide) and at 35i5 C 'for about 3 hours,

clarified, salted with sodiumsulfate and isolated as {in Examplefl to give the dye of formula:

O SO Na. -HO T0 G O1 NaOzS- some 7 V V 0 Example i V 25 parts of the dye base 'tureof 60 parts ofsodium sulfate and 60 parjts'of sodium chloride. The precipitated rubine dye of the structure is'filtered off and washediwith 300 partsofa sodium sulfate solution. The filter cake is pressed to about 30% dye content and dried at 80 C.

".Example' 7" 160 parts ofwater are stirred with 2,9parts of sodium bicarbonate and 22.3' parts of S-amino-Z-ethylaminobenzenesulfonic acid arse" C. vforl5minutes and cooled to 40 C. At this temperature are added 0.9 part'of cupric sulfate, 0.4 part of copper powder, and, slowly over a 2-hour period, 39.8 parts of the sodium salt of bromamine acid (1-amin0-4-bromo-2-anthraquinonesulfon-ic acid), The blue slurryis stirred for an additional 7 r is salted to 10% by volume'withsolid sodium sulfate over a 2-hourperiod, filtered, washed withl0% sodium,,

2 hours, dclarified, and then salted carefully to a 14% salt solution, using sodium chloride. The precipitated needles are filtered, Washed free of-the green-brown color "with'15% sodium chloride solutiong-and redissolved at 353 C. in 1500' parts of Water at'pH 7.6:02 (using sodium hydroxide); Tothis solution are added 60parts of xylene containing.24.2 parts of 2,3-dichloro-6-quinoxalinecarbonyl chloride, and, the pHand temperature are maintained at 5.5-8 (with-sodiumhydroxide) and "30- --C., respectively, until the pH-is} steady (usually-3 1 hours). The solutionis clarifiedby filtrationand the 35" filtrate. is slowly salted-to 4% with sodium chloride and "6% with sodium sulfate, which -aifords',; after stirring for 14 hours, agblue crystalline precipitate. 'The product i of the structure l filtered,washed with a solution of 4% sodium chloridev and 10% sodium sulfate, and dried at C.

'7 I Example'8 To 160 parts, of" chlorosulfonic acid cooled to 5 C.

are added 23 parts of copper phthalocyanine at such' a rate as not to exceed, 25 C. This slurry is :s'tirred' 15 at this temperature for 3.5 hours,

minutes, heated over 1.5 hours to i5 C.'and stirred lution'is cooled to room temperature and is drowned in a'mixture ofv ice and water below '5 C. The solid, which in 'wh1ch all substituents modified by x and y are primarlly is'collected by filtration and washed with 5 C. aqueous 1% hydrochloric acid solution, corresponds to a mixture of'compounds, of the structure 1 l CuPc j-locatedin the '3, 3', 3", and 3"" positions.

[ To 'this wejt sulfonyl chloride filtercake-slurried in 1200 parts of ice water are added 22.5 parts of 2,4-

diaminobenzenesulfonic acid, and the pH 'is adjusted to.

7.5 with ammonium hydroxide.- The mixture. isheated V to 40 C. and; stirred at this temperature,'maintaining the. pH at 73,-8.0, byadditionof ammonium hydroxide until the pH remains constant, usually 3-4.11ours. The

resulting dye base is filtered 'ofii after acidification of The dark green sothe solution to pH 2 with hydrochloric acid. After 0 UR:- (SOrNH b (SOr-NH- S0311);

is reslurried in 1500 parts of 45 C. water at pH 7.5-8.0 using sodium hydroxide. To this solution is added with vigorous stirring at 40-45 C. and pH 7.5-8.0 (ma-intained with sodium hydroxide) a solution of 2.1.0 parts of 2,3-dich1oro-6-quinoxalinecarbonyl chloride and 45 parts of xylene. After the pH holds constant, about 4 hours, the solution is clarified and 100 parts of sodium sulfate are added. The turquoise solution is salted carefully with solid sodium chloride to about 16%, the precipitated dye is filtered, washed with a sodium sulfate and 10% sodium chloride solution, and dried in an oven below 80 C. This dye mixture of the structure (SOaNah curc wmmrob soaNa N SmN-O 01 0 I 1k y c on analysis is found to contain 1.0 dichloroquinoxaline radical, 1.4 sulfamoyl radicals, and 2.5 sodium sulfonate groups. Thus, the values of a, b, and c are 1.5, 1.4, and 1.0, respectively. This dye is standardized to 55% active ingredients by the addition of anhydrous sodium sulfate. When applied to cellulosic textile materials by the procedures shown in the examples of Part 1 above, bright turquoise shades have good light and wash fastness are obtained.

Additional dyes applicable in the present invention are obtained by employing other dye bases in condensation with 2,S-dichloro-6-quinoxalinecarbonyl chloride according to procedures described in the above preparative Examples 1-8. For instance, the dye base used in Example 1 (3-amino-1,S-naphthalenedisulfonic acidmeta-toluidine) may be replaced by equimolar proportions of any of the following dye bases:

R=CH3, OHZCI,

CHg-SOaH HOaS SOQH

R'=H, CH3, omen.

wherein R HO-fl N t SIOKH SOQH HOsS- In Example 3, the following dye bases may be substi- 0 tuted for the dye base which was used therein:

mew

1'1 r 7 a -12 $0311 7 V V a V y -Ir1 Examplei-the dye baseis fermed by coupling .acetyl l n {acid (S-amino-1-naphthol-3,6 disulfonic acid) with Q NzN' I orthanilic acid. In place of this, dye -base, one can use 7 a equimolar proportions of the following dye bases: HO3S 5 V HOsS- R" S oan a v V i R"=C1, CH pSO H, -N&CH| M 15 a r r I a H Hz N fHOaS- l r H I 370 N= N all 7 I Q 7 'R Same as irnmediately above -R"=H, CH, CH CH, In Example 4, either'the couplerfor the diazo COIIIPO'. CHECK nent or both may bra-changed. For instance, the, 87 311111 101 2 CHgQHzOSOgH 1-naphtl1ol-3,6-di$ulfonic acid used in Example 4'may be' v V replaced with equimolar amounts of 1 :7

Moreover, a'dye can be formed according 1o che pro- ,;QI5a,v H

cedure of Example 4 if the orthanilie acid is replaced with r r i 3 3 equimolar amounts of a r a a a a r rl or 2- 808R y J j V v a Example 6 shows'a quinoxaline dye in 'wlaieh the dye chromophore is a radical of a metallized azo-coupling V '1 product of Z-aminp-l-pher1ol-4-Sulfionic acid 6-amino- N CHE-"S0311or V a 1-naphthol-3-s1flfonie.acid. .It is .possible'toslibstitutefor V y this dye base equlmolar parts-of oneor agrnixture of the 4 I a following metallized azo dye bases:

Azo DyeBase v Metallized with Cu or C0. 7

I Cu or Cr.

Azo Dye Base Metellized with N=N--CH;

IL u] 011. H03S SO3H 110- N OH HOaS- NHR' s O H '=H, CH CH CHQCHQCN v 01 ()H H? NH:

-N=N N=N Cu or Go or Cr.

HOaS- H3O HOaS- SOaH H2N- N=N-OH |L l 110- N HO IIIHQ N SOaH OH H0 8- I EzN- SOaH SOaH Substitutions can also be made for the lanthraquinone dye base of Example 7. The following anthraquinone 55 mterchangeably to form dye bases Whlch may be used components and diamine components can be condensed in place of the dye base which is specified in Example 7:

rtnthraquinone Component,

7 Component 0 IITH,

RHN

' 1 HOaS-QNH,"

(in-20112011" orn'crracN'.

' Theuse of a phthalocyanine dye base has been illustrated in Example 8. Typicalphthalocyanine dye bases which are 'useful in this example are prepared by react- V 7 ing a metal phthalocyanine trior tetrasulfonyl chloride wherein the .sulfo groups are in the 3, '4 or 3 and 4 positions and the metal is Cu, Ni, or Co,'with a diaminein the presence of a monoamine. The diamine used most frequently is a I i 1 R=H, em, on a p a CH3; OHEOHEON, ornornorr, 'omomoso n Ammonia is thepreferred monoamine, but other amines such as methylamine and fi-hydroxyethylamine are also useful. r

The preceding representative: examples may be varied within the scope of the present total specification discellulosic materials which process consists essentially of the following steps:

('1) the 'cellulosic materiatis padded with said fiberreactive dye from anjajqueous, s'olntion'iof saiddye,

'said solution being maintained at a pH-of from 6 '(2) thelresultingadye-padded'material is then treated for at least five seconds with an aqueous alkaline liquorv consisting essentiallyoffrorn- 2 to 15 g./l. of

sodium hydroxide and 20010300 gg/ l. of electro-- lyte selected from the group consisting of NaCl and Na SO the temperature ofsaid liquor being 160". to 218 F.; r t

(3 the dyed fabric 10f step ('2)"is then washed.

'2. .A'process" according to claim 1, step (1), Wherein urea isadded to, said dye solution.

3. A process according to claim'lwherein step (1) is followed by drying the dye-padded fabric prior to 7 step (2). t

n p 4 A process according'to claim :lpwherein step (1) is followed by drying the dye-padded fabric prior to step I (2), the aqueous alkaline liquor treatment of step ('2) closure, as understood and practiced, by one skilled in the art,- to achieve essentially the'same results.

As many apparently widely different, embodiments of 7 this invention may be made without departing from the spirit'and scope thereof', it is to be understoodthat this invention is notlimitedto the specific-embodiments thereof except as defined in the appended claims.

The embodiments of the invention in which an' exclusive property or privilege is claimed are definedi as fol lows: a a z t, 1, A process for applying fiber-reactive dyes 'whichcontain a 2,3-dichloro-6-quinoxalinecarbonylamino group to being conducted at "a temperature-within the range of .80-212 F. forv from 5 to 10 seconds. 7' j p ,7

Reterences Cited by the Examiner 'UNITED STATES PATENTS 1 ,886,480 11/32 Haller et al. 8-54.2 X 3,043,650 7/62 Wegmann et a1. 81.20 3,088,790 63 Schultheis etal 8-54.2 7 M FOREIGN PATENTSl 315,451 7/29 Great Britain.

1,247,660 10/60, France. 7 V

NORMAN G. TQRCHIN, Primary Exaininer. 

1. A PROCESS FOR APPLYING FIBER-REACTIVE DYES WHICH CONTAIN A 2,3-DICHLORO-6-QUINOXALINECARBONYLAMINO GROUP TO CELLULOSIC MATERIALS WHICH PROCESS CONSISTS ESSENTIALLY OF THE FOLLOWING STEPS: (1) THE CELLULOSIC MATERIAL IS PADDED WITH SAID FIBERREACTIVE DYE FROM AN AQUEOUS SOLUTION OF SAID DYE, SAID SOLUTION BEING MAINTAINED AT A PH OF FROM 6 TO 7.8; (2) THE RESULTING DYE-PADDED MATERIAL IS THEN TREATED FOR AT LEAST FIVE SECONDS WITH AN AQUEOUS ALKALINE LIQUOR CONSISTING ESSENTIALLY OF FROM 2 TO 15 G./1. OF SODIUM HYDROXIDE AND 200 TO 300 G./1. OF ELECTROLYTE SELECTED FROM THE GROUP CONSISTING OF NACL AND NA2SO4, THE TEMPERATURE OF SAID LIQUOR BEING 160* TO 218*F.; (3) THE DYED FABRIC OF STEP (2) IS THEN WASHED. 